Process for the recovery of unsaturated hydrocarbons



Patented Feb. 25, 1947 z,41t,t47

I PROCESS FOR THE RECOVERY OF UNSATURATED HYDROCARBONS Walter A. Schulze and John C. Hillyer, Bartlesville, Okla, assignors to Phillips Petroleum Company, a corporation of Delaware ApplicationFebruary 9, 1943, Serial No. 475,268

9 Claims. (Cl. 260683.2)

This invention directed to' a process for ob' I taining butadiene from hydrocarbons and relates further to a process'for separating butadiene and isobutene from hydrocarbon mixtures containing the same. More particularly,this process is concerned with the separation of valuable, easily polymerizable butadiene-isobutene mixtures from gas mixtures containing same in admixture with butane and butenes.

It is among principal objects of this invention to provide a simple and effective method for the preparation, concentration, separation and recovery of butadiene isobuten'e mixtures from gas mixtures in which these compounds "are formed or contained along with butene-1 and other hydrocarbons whose physical and chemical properties ordinarily render such separation difficult and complex. Further objects and advan tages of the present inventionzwill be readily apparent from a consideration of the factors discussed hereinbelow.

In our copending application, Serial No, 369.490, filed December 10, 1940 (now Patent Number 2,386,983, granted October 16, 1945) of which the present application is a continuation-in-part, we have disclosed-an improved method of separating butadiene from hydrocarbon mixtures, particularly those containing mono-olefinic C4 hydrocarbons. One of the steps in the process therein disclosed comprises isobutene removal either before or after segregation of a concentrated butadiene fraction. Said butadiene and isobutene-'- containing mixtures are normally present in C 4 hydrocarbon fractions produced by thermal or catalytic treatment of normally gaseous hydrocarbons or of heavier liquid petroleum fractions, and, especially in the latter instance, often contain large concentrations of isobutene.

"A Crhydrocarbon fraction of the type described may be readily isolated from higher and lower boiling fractions in substantially pure form by fractional distillation. Further. eparation of this complex fraction by distillation, however, has been diflicult since the boiling points of all the components of this fraction are distributed over a relatively narrow range, as indicated below:

.With emcient fractionating equipment it is tioned mixture.

side and jn-butaneand the-isomers of butene-2 on the higher boiling side, the'separation of butene-lfisobutene and b'utadiene'into substan-' tially pure components is almost impossible. As noted above, these three compounds boil within 3 F. Similarly, the separation of isobutene butadiene stocks from such mixtures also containing butene-1 is extremely 'diflicult.

We have now found that butadiene-isobutene concentrate may be separated from a C4 hydrocarbon mixture containing these components along with normal butene comprising at least butene-1 and C4 parafiins by a process compris 'ing the properselection and/or sequence of the steps of (1) removing isobutane byv fractionation, (2) isomerizing butene-1 to butene-2, (3) fractional distillation to give a butadiene-ism butene concentrate We have found that when butene-1 is absent or is reduced to very low concentrations, it is possible to prepare by simple fractional distillation a product consisting essentiall of butadiene and isobutene with smaller amounts of contaminants than has heretofore been possible except by the usually impracticable method of blending the substantially pure components. If compounds, which cannot be separated by fractionation. remain in the butadiene-isobutene mixturetin minor quantities after the first two steps. the final concentrations of butadiene and isobutene attained is related inversely to the quantityof these other hydrocarbons remaining. I V I We have also found that the conversion of butene-1 to butene-2 which is; readily accomplished by means of catalytic isomerization at low temperature offers a means whereby nearly all the normal butenes may readily be recovered by fractionation in the form of a butene-2 concentrate without excessive loss or contamination. v

The process according to our invention'may be more readily understood by referring to the ac companying drawing which represents schematically one type of apparatus in which our process can be used.

In the drawing, a C4 hydrocarbon fraction containing butene-1, isobutene and butadiene, such as that derived'from cracking still vapors, dehydrogenation of normal butane or butenes or similar processes, enters the system vialine I if it contains isobutane which is removed via line. 2 in fractionatort, or via line 4 if it is free from isobutane, and passes via line 5 and preheater 6 5 into catalyst case I in whichlisomerization of possible to effect satisfactory separations between a certain of the C4 hydrocarbons of the above-mensuitable heat and pressure, the overhead passbutene-l to butene-2 is carried out. The isomerization efiiuent passes vialine 8 to condenser 9 from which. the liquid is passed via line [0 to fractionating unit ll whereby the application of 'In such" equipment, while it is I possible to separate isobutane on the lower boiling jing through line l2 consists of butadiene-isolbutene and small portions Of'j'UIICOHVBItGd butene-l whilethe bottoms fraction leaving via line l3 contains principally butenes-2, together with normal butane, where that component was prest. 3 ent in the-incoming feed.

The overhead from column Himayibe with-' Qdrawn via line Hi. If desired, it maybe given a second isomerization treatment :by -;passage via line I5 and heater [6 to a secondcaltalyt-i'clisomerization converter I! where the butene-l is-converted to butene-Z. The vaporous efiiuentirom converter I1 passes to condenser 18 from which f the liquid condensate is fed to a second'ff-ractionator !9 from which an overhead of butadiene- I isobutenerand -a ebottomseaf bntene=2 are .with- 1 drawn.

-Inpne specific .lembodiment .10: v the .invention,

1 the 0.4 inaction, containing .butenes, ibutadiene and: isobutene is fde-isobutanized, sand passed in I the vapor iorm overza catalystaofnan vacidichnature, such as dilute ,phosphoric {acid .supported omaninert-narrierisuchtast silica.gel,.,at a tem- 1 peraturesin therangeof 20,0 to {600 Faandoat flow rates equivalent .-to :05 to 5 liquidvolumes per vhourper volume .of ;catalyst, to isomerize 'butene-l to .butene-.2. ,The vapors ,areicooled, 1 condensed. an.d..then .-subjected toiractional .dis-

tillation in .which an .overheadiraction .of "butadiene .-and.isobutene.and a.- bottom. fraction nomi prising -.butene-Q isomers is=.ob.tained.

The visomerization :reaction ,is based on .the

tures. The means whereby this substantially complete isomerizationrof buteneelt' is carried out to butene Z-m'ay be selectedatwill from-a variety of methods, using one of the many different catalysts known to the art. a

Following the steps of isomerization of butene .l,:the.C4 mixture comprises essentially butadieneisobutene, n-butane and the isomers of butene- 'This1fraction is well adapted to fractional "distillationior segregation of butadiene and isobutene-since the :boiling point of the butadiene differsby ,8;E. .or,more from the boiling points of the other hydrocarbons present.

The :butadiene-isobutene stream removed is highly concentrated, the exact composition depending-on,the.initialeconcentrationsief zthe defact "that lbutene-l exists ,in...equilibrium with t j butenes-.2, and that :the. relativeiamounts .of .the

isomers present varies with the temperature. We have .found thatlow temperatures favor-the butene-2 isomers tas eagainStrbutene-LI, and that in. processes for-carryingeoutthel isomerizationof butene-l temperatures lshouldlbe ikept as low. as practicable and a catalyst should Joe employed to obtain rapid rreaction. The -selection of an operating temperature is .dependent, .of course,

on additional .,factors, particularly .the (activity of the catalyst [and ;.the..extent.of.11ndesirable side reactions occurring. We Lhaveiound ;that seven in the presence of ...c atalysts, reaction proceeds slowly Ebelow 100 and. temperaturessofl 150 .to 600 or eyen .hi herare desirable. In .the isomerization step, splitting and coking reactions are unimportant at temperatures, within thisrange,anmpolymerization of the. olefins.,to

form octenes or ,theLJike -may Jaeieffectively $111 presse by suitable -control,..of; catalyst compositioniand .treating conditions.

.As catalysts i or our :isomerizationr-s'tep 1 we prefer to employ catalysts which. are highly active so that lower isomerization "temperatures may be employed. Acidic .salts such as aluminum phosphate and the like may be used. Even more active, however, are solutions of sulfuric or phosphoric acids adsorbed on suitable'carri'ers whereby,thelaoidstrengthismaintained'atlvalues below the range .which would :cause polymerization iofthe'butadiene. "Also preferred are catalysts comprising magnesia, particularly brucite,

which are activated by 'substantially complete dehydrationprior to use and are employewwith dehydrated feed. stocks. 7

- It, is not to be sunderstoodffrom j the foregoin description of one specific .method of carrying out the .,.'isomerization of "butane-l to biltenI-i? thereto. Thisinvent-ion. contemplates the use of catalytic isomerization asthe. first step in aiprocess .of concentratin butadiene 'isobntene .imix- .thattthejapplication of the invention is limited sired components .:and .the completeness which buteneel wasremoyedprior Eton-fractionation. in general, 2' from predominantly vainsatu rated gases containing initiallymore than rten per centof butadiene .andiso-butene, concentrates of. ;9.0 ;per .cent {and above "may the obtained. From gases containing =initially ;-a greater 1 quantity of butadiene and/or isobutene -suchrasthose obtained: from gas cracking/having 130' to :50 per cent .butadiene :and isobutene and rnegligible amounts of,n butaneiconcentrates.of:;per cent .or even higher :are obtained.

This gprocessmay-very iconvenl'ently be "applied to dshe =process "of x-cataiytically' #cracking ihydrotion. In "some cases the *isomerization treatment may *be performed "after an "initial frac: tionation to separate butene=2 and/or n-butane.

"Many :modificati'ons of "our process :are 'po's s'ible, depending on th'eparticular hydrocarbon 'mixture undergoing 'treatment .and the most efiicient combination or *seguencaof tthesteps of said process. Thus nmemisobutane is'fsubstantially absent. iromia mixture, the .de-isobutaniz ing step, may be .omitted, .andiisomerizationl alone .followed by .Ifraction'ation will produce -'.a "highpurity lbutadiene-isobutene concentrate. ..Also.

successive treatments-ref the. loutadieneisobutene 'fraction. by ourprocesslorlby any individual steps thereof to.- increase vthe purity .of .the concentrate may be desirable. {For example, lairactionsconsisting of butene-l, isobutene and but-adiene and producedby our process may be given a second :isomerization treatment and "refractionated toremove .themajor portionflofwtheinormalxnonoolefins. These and other modifications .of --.our

process will be txbvious to those skilled in the art and thus are within the scope of our invention; I The butadiene-isobutene concentrate prepared in accordance with the, process of the present; -invention.;may be particularly suited as :a :charge for polymerization to that form of synthetic rubber known as butyl rubber. Howevenvit maybe put to any other usewithin the skill of those versed in "the art "andj'the v'invention, thereiorel,

is by no means limitedto preparation of a butyl rubber feed.

The following example will still further illustrate specific applications of theprocess of the present invention, and is not to be construed as limitations thereof.

Example Component Weight per cent Iii-Butane b- MH ol r m i s Ohm-s w Isomerization of this fraction at 250 F. over 50 per cent phosphoric acid supported on silica gel converts butene-l to butene-2 with the efliuent having the following approximate composition:

Component Weight per cent Butadiene. 12. 6 Isobutene. 24.0 Butenc-L- 4. 2 Butene-ZL. 47. 9 n-Butane 11. 4

Fractionation of the isomerized C4 mixture produces an overhead fraction containing substantially all of the 'butadiene and isobutylene with only a minor quantity of other olefins.

Further concentration of the butadiene-isobutene stock by separation of butene-l is obtained by a second isomerization treatment over a catalyst of low polymerizing activity followed by fractionation to remove the butene-2 formed in isomerization.

In the foregoing specification and in the claims, the butene-2 referred to ordinarily describes either or both butene-2 isomers in proportions which depend on the material being treated and the conditions under which said isomers are formed. For purposes of convenience, therefore, the term butene-2 Will describe a portion containing either or both of said isomeric forms.

While we have described our invention in a detailed manner and provided specific examples illustrating suitable modes of executing the same, no limitations are thereby implied other than those imposed by the v appended claims.

We claim:

1. A process for the separation of a butadieneisobutene concentrate from a C4 hydrocarbon mixture comprising n-butane, butadiene, isobutane, butene-l and isobutene, which comprises fractionating said mixture to remove isobutane, contacting the de-isobutanized mixture with an olefin isomerization catalyst under suitable condition and therebyv converting butene-l to butene-2, and subjecting the isomerized mixture to fractional distillation to produce an overhead fraction comprising butadiene and isobutene and a bottoms fraction comprising n-butane and butene-2.

2. A process for the separation of a butadieneisobutene concentrate from a C4 hydrocarbon mixture comprising n-butane, isobutane, bu-

6 tadiene, bu'tene-l and isobutene, which com-' prisesfractionating said mixture to remove iso-" butane, contacting the de-isobutanized mixture with an olefin isomerizationca'talyst and there- I by converting butene-l to butene-2, andfractionally distilling the resulting mixture to produce an overhead fraction comprising butadieneisobutene .and a bottoms fraction comprising n-butane and butene-2. 3. A process for the separation of a butadieneisobutene concentrate from a C4 hydrocarbon mixture containing n-butane, butadiene, isobutene, and butane-1 which comprises contacting said mixture with an olefin isomerization cata-. lyst and thereby converting buten'e-11 to butene-Z, and fractionally distillingthe resultingnmixture to produce an overhead-fraction. comprising 'butadiene-isobutene; and a bottoms fraction com: prising n-butane and butene-2.; V

4. A process for theseparationof a butadieneisobutene concentrate from a C hydrocarbon mixture containing 'n-butane, butene-l, isobuitone and butadiene which comprises contacting said mixture with an olefin isomerization catalyst under conditions effecting conversion of a substantial proportion of the butene-l to butane-2, fractionally distilling the resulting mixture to produce an overhead fraction comprising butadiene, isobutene and the unconverted butene-l and a bottoms fraction comprising n-butane and butene-2, treating said overhead fraction in a second catalytic isomerization stage under conditions effecting conversion of a further and substantial amount of butene-l to butene-2, and finally fractionally distilling the efliuents of the second isomerization step to produce an overhead fraction substantially comprising a butadiene-isobutene mixture and a bottoms fraction comprising butene-2.

5. In the proces of producing butadiene by prises the steps of catalytically isomerizing said mixture under conditions eilecting conversion of butene-l to butene-Z, and subjecting the resulting mixture to fractional distillation to produce an overhead fraction'comprising butadiene-isobutene and a bottom fraction comprising butone-2.

6. A process for the separation of a butadieneisobutene concentrate from a C4 hydrocarbon mixture comprising n-butane, butadiene, isobutane, butene-l, and isobutene which comprises fractionating said mixture to remove isobutane, isomerizing a substantial proportion of the hutene-1 to butene-Z, subjecting the mixture to fractional distillation to produce an overhead fraction comprising butadiene, isobutene and unconverted butene-l and a bottoms fraction comprising n-butane and butene-2, treating said overhead fraction in a second isomerization stage under conditions elfectin conversion of a further and substantial proportion of the butene-l to butene-2 and finally fractionally distilling the eiiluents of the second isomerization step to produce an overhead fraction substantially comprising a butadiene-isobutene mixture and a bottoms fraction comprising butene-2.

7. A process for the separation of a butadieneisobutene concentrate from a C4 hydrocarbon 7 ing :a sulistantial proportion of the'ibutene-lto but'ene-2, subjecting the mixture to fractional distillation to produce an overhead fraction comprising butadiene, :isobuteneiand unconverted butene-l-and a. bottomsfractioncomprising n-bu'- andisobutene and '21 'bottoms fraction comprisingdauteneez 7 1-8; .:A process fOI'lthBSSB ation of-abutadieneisobutene' concentrate from a U4 hydrocarbon mixture also containing butene-l "which 7 comprises subjecting said ieed tocatalytic:isom'eiiza-v tion under condition -effecting:conversion of said *buteneq to =butene-2 without; appreciably affecting the 'butadiene-and isobuteneeontent or the feed, and fractionally distilling the i'somerized mixture to produce :an' overhead ira'cti'on con! taming butadiene and isobutene and a' bottoms' fraction containing buten'e-Z.

9. The process of separation of butadieneand isobutene from a'dmixturewith butene-l. which comprises catalytically isomerizing the butane- 1 in said. mixture to butane-land fractionally distilling the isomerized mixture to separate .the butadiene and isobut'ene in an overhead fraction.

WALTER A. SCHULZEI JOHN C'.

REFERENCES CITED UNITED STATES PATENTS Number Name Date 2,298,931 Drennan Oct. 13, 13342 20 2,220,693 Van Peski et a1. Nov."5, 1940 2,299,716 Van Peski Oct 20,1942 Drennan .s Sept. 21, 1943 

